Certain 4-oxo-3-benzoylvalerolactones and thiolactones

ABSTRACT

Compounds having the formula ##STR1## wherein X is oxygen or sulfur; 
     R is halogen; C 1  -C 2  alkyl; C 1  -C 2  alkoxy; nitro; cyano; C 1  -C 2  haloalkyl; or R a  SO n  -- wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; 
     R 1  is hydrogen or C 1  -C 4  alkyl; 
     R 2  is hydrogen or C 1  -C 4  alkyl; 
     R 3  is hydrogen or C 1  -C 4  alkyl; 
     R 4  is hydrogen or C 1  -C 4  alkyl; or 
     R 3  and R 4  together form a single bond; or 
     R 1  and R 3  together are alkylene having 2-5 carbon atoms; or 
     R 2  and R 4  together are alkylene having 2-5 carbon atoms; and 
     R 5  and R 6  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  -- wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)-- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; or (12) --SO 2  NR c  R d  wherein R c  and R d  are as defined; and (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined and their salts are useful as herbicides.

This is a divisional of application Ser. No. 871,975, filed June 9, 1986, now U.S. Pat. No. 4,741,755.

BACKGROUND OF THE INVENTION

The compound having the structural formula ##STR2## wherein the nitro substituent is in the 3- or 4-position are described in J. Heterocyclic Chem., 6(1), pp. 13-22 (1969). No utility for these compounds is taught.

Compounds of the structural formula ##STR3## wherein X is halogen, CF₃, alkyl, nitro, cyano or alkoxy are described in European Patent Application Publication No. 40 082 (1981). The compounds are intermediates for the preparation of certain substituted oxonicotinates.

DESCRIPTION OF THE INVENTION

This invention relates to certain 4-oxo-3-benzoylvalerolactones and thiolactones and their salts and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprising an herbicidally active 4-oxo-3-benzoylvalerolactone or thiolactone and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl or R^(a) SO_(n) -- wherein R^(a) is C₁ -C₂ alkyl, preferably methyl and n is the integer 0 or 2, preferably 2; and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano or trifluoromethyl. The 5- and 6-positions of the 4-oxo-valerolactone or thiolactone moiety can be substituted, preferably with the groups hereinafter recited. The 3-, 4-, 5- and 6-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compounds having the following structural formula ##STR4## wherein

X is oxygen or sulfur;

R is halogen, C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; or R^(a) SO_(n) -- wherein R^(a) is C₁ -C₂ alkyl, preferably methyl and n is the integer 0 or 2, preferably 2;

R¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R¹ is hydrogen or methyl;

R² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl most preferably R² is hydrogen or methyl; or

R³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R³ is hydrogen or methyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁴ is hydrogen or methyl; or

R³ and R⁴ together form a single bond; or

R¹ and R² together are alkylene having 2-5 carbon atoms; or

R² and R⁴ together are alkylene having 2-5 carbon atoms;

R⁵ and R⁶ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and R^(b) is (a) C₁ -C₄ alkyl, preferably methyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) --N(R^(C))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isobutyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens are replaced by chlorine, bromine, iodine or fluorine.

Preferably, R⁵ is in the 3-position. Most preferably R⁵ is hydrogen or C₁ -C₄ alkoxy. Preferably R⁶ is in the 4-position. More preferably, R⁶ is hydrogen, chlorine, cyano, fluorine, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the subject of the instant invention.

The compounds of this invention can have the following three structural formulae because of tautomerism: ##STR5## wherein X, R, R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above.

The circled proton on each of the three tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following three resonance forms: ##STR6## wherein X, R, R¹, R², R³, R⁴, R⁵ and R⁶ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees of association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR7## wherein X and R through R⁶ are as defined and Y is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR8## wherein R, R⁵ and R⁶ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the lactone or thiolactone and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.

The reaction product is worked up by conventional techniques. ##STR9## wherein X and R through R⁶ are as defined.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins iof benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propiionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is acetonitrile. Other solvents which can be employed, depending on the reactants or products include toluene, 1,2-dichloroethane, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR10## wherein R, R⁵ and R⁶ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are four representative examples of the methods described therein. ##STR11## wherein R, R⁵ and R⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR12## wherein R, R⁵ and R⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventionaltechniques. ##STR13## wherein R, R⁵ and R⁶ are as defined and X is chlorine, bromine or iodine.

The substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.

The above-described valerolactones or valerothiolactones can be prepared according to the teaching of K. Schweiger, Monatshefte fur Chemie, 113, 1283 (1982); N. Bellara et al., J. Het. Chem., 15, 1153 (1978); and H. Meyer and D. Seebach, Liebig's Ann. Chem., 2261 (1975).

The following example teaches the synthesis of a representative compound of this invention.

EXAMPLE 1 3-(2'-Nitrobenzoyl)-6-methyl-4-oxovalerolactone ##STR14##

6-Methyl-4-oxovalerolactone (2.6 g, 20 mmol) and 2-nitrobenzoylchloride (3.8 g, 20 mmol) were dissolved in 30 ml methylene chloride and stirred at room temperature. Triethylamine (2.2 g, 20 mmol) in 20 ml methylene chloride was added dropwise, and the resulting mixture was stirred for 2 hours. The reaction mixture was then poured into 1N HCl and extracted with additional methylene chloride. The organic layer was then washed with 5% K₂ CO₃, brine, then dried with MgSO₄ and evaporated to yield an oil (4.2 g, 76%) which was used without further purification.

Two and sixty-seven one-hundredths grams (10 mmol) of the prepared enol ester was dissolved in 50 ml acetonitrile and stirred at room temperature. Triethylamine (2.0 g, 20 mmol) and acetone cyanohydrin (0.1 g, 1 mmol) were added all at once, and the resulting mixture stirred for 5 hours. The solvent was evaporated and the resulting oil dissolved in ether. The organic liquid was then washed with 1N HCl, brine, dried with MgSO₄ and evaporated to yield an oil which crystallized on standing (2.3 g, 86%, m.p. 84°-89° C.) which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I                                      __________________________________________________________________________      ##STR15##                                                                     Comp.                                                                          No. R  R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                           R.sup.5                                                                            R.sup.6                                                                              X m.p. °C.                                  __________________________________________________________________________      1  Cl H  CH.sub.3                                                                          bond H   4-Cl  O 126-128° C.                                2  Cl H  CH.sub.3                                                                          H H  H   4-Cl  O oil                                               3  NO.sub.2                                                                          H  CH.sub.3                                                                          H H  H   4-Cl  O oil                                              .sup.  4.sup.a                                                                     NO.sub.2                                                                          H  CH.sub.3                                                                          H H  H   H     O 84-89                                             5  Cl H  CH.sub.3                                                                          H H  H   4-SO.sub.2 CH.sub.3                                                                  O oil                                               6  CH.sub.3                                                                          H  CH.sub.3                                                                          H H  H   4-Br  O 93-96                                             7  CH.sub.3                                                                          H  CH.sub.3                                                                          bond H   H     O brown semi-solid                                  8  Cl H  CH.sub.3                                                                          bond H   4-Cl  O 94-102                                            9  Br H  CH.sub.3                                                                          bond H   H     O oil                                              10  Cl H  CH.sub.3                                                                          bond 3-NO.sub.2                                                                         H     O oil                                              11  CH.sub.3                                                                          H  CH.sub.3                                                                          bond H   4-Br  O 106-110                                          12  Cl H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-NO.sub.2                                                                           O 92-96                                            13  Cl CH.sub.3                                                                          CH.sub.3                                                                          H CH.sub.3                                                                          H   4-NO.sub.2                                                                           O 72-76                                            14  Cl H  *  H *  H   4-SO.sub.2 CH.sub.3                                                                  O 102-105                                          15  Cl H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-SO.sub.2 CH.sub.3                                                                  O 122-126                                          16  Cl CH.sub.3                                                                          CH.sub.3                                                                          H CH.sub.3                                                                          H   4-SO.sub.2 CH.sub.3                                                                  O oil                                              17  Cl CH.sub.3                                                                          CH.sub.3                                                                          H CH.sub.3                                                                          H   4-Cl  O 145-149                                          18  Cl H  *  H *  H   4-NO.sub.2                                                                           O oil                                              19  NO.sub.2                                                                          H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-Cl  O oil                                              20  NO.sub.2                                                                          H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-Cl  S --                                               21  Cl H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-SO.sub.2 CH.sub.3                                                                  S 166-170                                          22  Cl H  CH.sub.3                                                                          H CH.sub.3                                                                          H   4-Cl  S 142-143                                          __________________________________________________________________________      .sup.a Prepared in Example 1.                                                  * = CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2-                                 

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test: On the day preceding treatment, seeds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The weeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea) and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                         ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.    FT     WG      WO   AMG   VL    MD   YNG                                ______________________________________                                          1     95     70      45   10    100   100  50                                  2     95     90      10   75    100   95   95                                  3     100    100     80   90    100   100  80                                  4     100    100     70   95    100   100  80                                  5     100    100     5    100   100   100  80                                  6     100    100     10   90    100   100  80                                  7     0      0       0    0     0     0    0                                   8     100    10      100  100   100   100  80                                  9     100    10      70   20    95    95   0                                  10     20     0       0    10    10    60   0                                  11     100    60      60   40    100   100  80                                 12     20     50      0    60    100   100  0                                  13     20     100     0    10    90    100  70                                 14     0      30      0    50    100   100  80                                 15     80     95      20   50    95    100  80                                 16     100    100     50   60    85    100  80                                 17     80     80      0    0     85    90   80                                 18     0      40      0    5     80    80   20                                 19     100    100     90   95    100   100  80                                 20     80     95      0    100   100   100  80                                 21     80     100     0    100   100   100  80                                 22     30     80      0    100   100   100  80                                 ______________________________________                                    

Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III                                                        ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.    FT     WG      WO   AMG   VL    MD   YNG                                ______________________________________                                          1     95     55      40   70    100   100  65                                  2     75     75      10   75    100   65   75                                  3     70     80      80   50    80    95   80                                  4     100    100     85   50    90    90   70                                  5     100    95      80   80    100   100  30                                  6     75     40      0    100   100   100  30                                  7     10     0       10   60    90    10   0                                   8     85     30      85   100   100   65   80                                  9     50     10      0    10    90    100  0                                  10     0      0       0    30    80    80   0                                  11     60     40      30   100   100   100  60                                 12     10     30      0    20    60    90   30                                 13     0      60      0    20    50    50   0                                  14     0      60      0    20    50    50   30                                 15     10     70      20   80    90    100  70                                 16     50     50      50   80    50    50   30                                 17     30     50      0    60    80    80   33                                 18     0      0       0    5     5     5    0                                  19     95     100     80   100   100   100  80                                 20     0      30      0    40    80    80   30                                 21     0      50      0    90    90    100  50                                 22     0      50      0    80    90    100  50                                 ______________________________________                                    

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or whih may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as destrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    __________________________________________________________________________     General Formula with Ranges                                                                      Specific Formula                                             __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          Herbicidal compound                                                                        5-55  herbicidal compound                                                                         24                                              surfactant(s)                                                                              5-25  proprietary blend of oil-                                                                   10                                              solvent(s)  20-90 soluble sulfonates and                                                   100%  polyoxyethylene ethers                                                         polar solvent                                                                               27                                                                petroleum hydrocarbon                                                                       39                                                                             100%                                            WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                        3-90  herbicidal compound                                                                         80                                              wetting agent                                                                              0.5-2 sodium dialkyl naphthalene                                                                  0.5                                             dispersing agent                                                                           1-8   sulfonate                                                    diluent(s)  8.5-87                                                                               sodium lignosulfonate                                                                       7                                                           100%  attapulgite clay                                                                            12.5                                                                           100%                                            EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                        1-20  herbicidal compound                                                                         10                                              binding agent                                                                              0-10  lignin sulfonate                                                                            5                                               diluent(s)  70-99 calcium carbonate                                                                           85                                                          100%               100%                                            FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                        20-70 herbicidal compound                                                                         45                                              surfactant(s)                                                                              1-10  polyoxyethylene ether                                                                       5                                               suspending agent(s)                                                                        0.05-1                                                                               attagel      0.05                                            antifreeze agent                                                                           1-10  propylene glycol                                                                            10                                              antimicrobial agent                                                                        1-10  1,2-benzisothiazoline-3-one                                                                 0.03                                            antifoam agent                                                                             0.1-1 silicone defoamer                                                                           0.02                                            solvent     7.95-77.85                                                                           water        39.9                                                        100%               100%                                            __________________________________________________________________________

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR16## wherein X is oxygen or sulfur;R is halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; nitro; cyano; C₁ -C₂ haloalkyl; or R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl; R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together form a single bond; or R¹ and R³ together are alkylene having 2-5 atoms; or R² and R⁴ together are alkylene havin 2-5 atoms; and R⁵ and R⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined and their salts.
 2. The method of claim 1 wherein X is oxygen; R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -CA₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ and R⁶ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N--(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 3. The method of claim 2 wherein R⁵ and R⁶ are independently are hydrogen; chlorine; fluorine; bromine; methyl; methoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- wherein n is the integer 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, or n-propyl; --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; R^(e) C(O)-- where R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁵ is in the 3-position and R⁶ is in the 4-position.
 4. The method of claim 2 wherein R⁵ is hydrogen and R⁶ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, cyano or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 5. The method of claim 1 wherein X is sulfur, R is chlorine, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is methyl, R⁵ is hydrogen and R⁶ is 4-SO₂ CH₃.
 6. The method of claim 2 wherein R is nitro, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is hydrogen, R⁵ is hydrogen and R⁶ is hydrogen.
 7. The method of claim 2 wherein R is nitro, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is hydrogen, R⁵ is hydrogen and R⁶ is 4-chlorine.
 8. The method of claim 2 wherein R is chlorine, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is hydrogen, R⁵ is hydrogen and R⁶ is 4-SO₂ CH₃.
 9. The method of claim 2 wherein R is CH₃, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is hydrogen, R⁵ is hydrogen and R⁶ is 4-bromine.
 10. The method of claim 2 wherein R is chlorine, R¹ is hydrogen, R² is methyl, R³ is hydrogen, R⁴ is hydrogen, R⁵ is hydrogen and R⁶ is 4-chlorine.
 11. The method of claim 2 wherein R⁵ is hydrogen.
 12. The method of claim 3 wherein R⁵ is hydrogen. 